Patent GB-1074065-A (GB)
Title: Method of producing reduced transition metal halide, polymerization catalysts containing it and process for the polymerization of ª-olefins with such a catalyst
IPC: C08F4/68
Filed: 1964-06-11
Abstract: Chlorides, bromides, and iodides of Ti, Zr, V, Mo, W, or Cr, in which the metal is in a lower than normal valency state are made by reducing one or more of the above halides in which the metal is in its maximum normal valency state, with a metal from Group I of the Periodic Table in the presence of a complexing agent which forms a complex with the halide of the metal formed in the process and also acts as a solvent for the complex.  The metals may be used in conjunction with a coreducing agent selected from alkyl, phenyl, or hydrides of a Group Ia, II, or IIIa, metal, and the complex hydride, alkyl, or phenyl derivatives of aluminium and an alkali metal.  The Group I metal is preferably Na, K, or Li, or an alloy of two of these metals with one another or an alloy of one of them with Al.  The complexing agent is preferably a diaryl ether, e.g. diphenyl ether but other agents such as amides, ketones, esters, phenols, nitro- and nitrile-containing compounds, organic sulphur compounds, and organophosphorus compounds may be employed.  In Example I, TiCl3 is made by reacting TiCl4 in a eutectic mixture of diphenyl ether and biphenyl with Li3Al, in Example II, VCl4, ZrCl4, MoCl5, WCl6, and CrCl3 alone or in admixture are reduced as in Example I, in Example III, TiCl3 is made by reacting TiCl4 with an alloy of Na and K in a solution of hexamethylphosphoric triamide in toluene, the triamide can be replaced by a solution of triphenylphosphine oxide in cyclohexanone or in benzonitrile, whilst in Example IV, TiCl3 is made by the procedure of Example I but sodium sand dispersed in toluene is used instead of Li3Al.  The reduced transistion metal halide is used as a component in a Ziegler-Natta-type polymerization catalyst.ALSO:Polymers of 1-olefinically unsaturated hydrocarbons are made by polymerizing one or more of the hydrocarbons, in bulk, or in an inert liquid diluent in the presence of a Ziegler-Natta type polymerization catalyst in which one component is a chloride, bromide, or iodide of Ti, Zr, V, Mo, W or Cr in which the metal is in a lower than normal valency state, and which has either been made by (1) reducing one or more of the above halides in which the metal is in its maximum valency state with a metal from Group I of the Periodic Table in the presence of a complexing agent which forms a complex with the halide of the Group I metal formed in the process, and also acts as a solvent for the complex, or (2) is a mixture of one of the above reduced transistion metal halides with a complex of a halide of a metal of Group I and a complexing agent which is also a solvent for the complex. The hydrocarbon may be ethylene, propylene, butylene, styrene, butadiene, isoprene, 1,3-pentadiene, 3-methyl-1-butene, 4-methyl-1-pentene, or allyl cyclohexane.  The other component is selected from (a) metals of Groups I(A), II(A), II(B) or III(A) of the Periodic Table, and hydrides and organometallic compounds thereof, or a complex metal hydride of aluminium and an alkali metal, or (b) an organoaluminium halide of the formula RmAlXn or R3Al2X3 wherein R represents an alkyl, cycloalkyl, phenyl or tolyl radical, X represents chlorine or bromine and m and n are integers whose sum is equivalent to the valency of aluminium, or (c) a polymeric reaction product of aluminium and a methylene halide. The exemplified catalyst is TiCl3 and (C2H5)3Al. The polymers are recovered by known methods.